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Frost, Ray L. and Hales, Matthew C. and Locke, Ashley J. and Kristof, Janos and
Horvath, Erzsebet and Vagvolgyi, Veronika (2008) Controlled Rate Thermal
analysis of hydromagnesite. Journal of Thermal Analysis and Calorimetry
92(3):pp. 893-897.

Copyright 2008 Springer

The original publication is available at SpringerLink http://www.springerlink.com

Controlled Rate Thermal analysis of hydromagnesite

Veronika Vgvlgyi, a Ray L. Frost, b Matthew Hales, b Ashley Locke, b Jnos
Kristf, a Erzsbet Horvth c
a

Department of Analytical Chemistry, University of Pannonia, H8201 Veszprm, PO

Box 158, Hungary

Inorganic Materials Research Program, School of Physical and Chemical Sciences,

Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane,
Queensland 4001, Australia

Department of Environmental Engineering and Chemical Technology, University of

Pannonia, H8201 Veszprm, PO Box 158, Hungary

Abstract
The reaction of magnesium minerals such as brucite with CO2 is important in
the sequestration of CO2. The study of the thermal stability of hydromagnesite and
diagenetically related compounds is of fundamental importance to this sequestration.
The understanding of the thermal stability of magnesium carbonates and the relative
metastability of hydrous carbonates including hydromagnesite, artinite, nesquehonite,
barringtonite and lansfordite is extremely important to the sequestration process for
the removal of atmospheric CO2. This work makes a comparison of the dynamic and
controlled rate thermal analysis of hydromagnesite and nesquehonite. The dynamic
thermal analysis of synthetic hydromagnesite proves that dehydration and
dehydroxylation take place in two steps at 135 and 184C, and decarbonation at
412C and 474C. Controlled rate thermal analysis shows the first dehydration step is
isothermal and the second quasi-isothermal at 108 and 145C, respectively. The
carbon dioxide is evolved in an isothermal decomposition at 370C. CRTA
technology offers better resolution and a more detailed interpretation of the
decomposition processes of magnesium carbonates such as nesquehonite via
approaching equilibrium conditions of decomposition through the elimination of the
slow transfer of heat to the sample as a controlling parameter on the process of
decomposition.
Keywords:

hydromagnesite, lansfordite, nesquehonite,

analysis, CRTA, thermogravimetry

magnesite,

thermal

Introduction
The thermoanalytical studies of basic hydroxy-carbonates such as magnesite
are not new, even though the first reported studies were in 1910 [1-9]. A similar lack
of recent studies is true of minerals such as hydroxyzincite and hydromagnesite [1-3,
5, 10-14]. There is a need to undertake a systematic study using the latest technology
of carbonate and hydroxyl-carbonate minerals using thermo-analytical techniques
including dynamic and controlled rate thermal analysis . Very few thermo-analytical
[9, 15] and spectroscopic studies of the hydroxy carbonates have been forthcoming
and what studies that are available are not new. Few Raman studies of any note are
available [16, 17]. To the best of the authors knowledge few recent thermo-analytical
studies of hydromagnesite have been undertaken [1, 4], although differential thermal
analysis of some related minerals has been published [12] .The decomposition of
aurichalcite, hydrozincite and hydromagnesite may result in the formation of metal
oxides or a mixture of metal oxides such as CuO and ZnO. Both these oxides may
function as catalysts and photo-catalysts. The thermal activation of aurichalcite results
in the formation of the oxide mixture, mixed at the molecular level and not at the
particle level.
Hydromagnesite
Mg5[(CO3)4(OH)2].4H2O
is
a
low
temperature
hydrothermally formed mineral [18-20]. Under natural conditions hydromagnesite
may form in evaporites depending on the availability of the Mg2+ ions in solution in
relation to the availability of other cations such as Ca2+ [18]. The highly hydrated
nature of the Mg2+ ion prevents the formation of anhydrous MgCO3 phases [19].
Additionally hydromagnesite can form as efflorescences on existing carbonate rocks,
man-made bricks and mortars, serpentinites, volcanic breccias and even meteorites
[21-25]. The conditions of formation are claimed to be independent of the carbon
dioxide partial pressure [18]. The mineral is also formed in caves from water that has
seeped through Mg-rich rocks [25]. The formation of carbonates such as
hydromagnesite may be a key to the sequestration of carbon dioxide [26, 27] i.e. the
removal of green house gases from the atmosphere.
Recently thermogravimetric analysis has been applied to some complex
mineral systems [28-41] and it is considered that TG-MS analysis may also be
applicable to many carbonate minerals [32, 42-46]. Raman spectroscopy has proven
very useful for the study of minerals [47-49]. Indeed, Raman spectroscopy has proven
most useful for the study of diagenetically related minerals as often occurs with
carbonate minerals [50-54]. Some previous studies have been undertaken by the
authors using Raman spectroscopy to study complex secondary minerals formed by
crystallisation from concentrated carbonate solutions [55].
The study of the carbonates of magnesium is of extreme importance in the
development of technology for the removal of green house gases. Magnesium
minerals such as brucite, periclase and hydrotalcites have the potential for the
sequestration of carbon dioxide. The formation and reaction pathways of hydroxy and
hydrous carbonates of magnesium is essential for the understanding of this
sequestration. The hydration-carbonation or hydration-and-carbonation reaction path
in the MgO-CO2-H2O system at ambient temperature and atmospheric CO2 is of
essential significance from the standpoint of carbon balance and the removal of green
house gases from the atmosphere. A better understanding of the global masses of Mg

and CO2 and the thermal stability of the hydrated carbonates of magnesium will
provide a practical understanding for carbon dioxide removal. From a practical point
of view, the exact knowledge of the reaction path in MgO-CO2-H2O system is of great
significance to the performance of brucite and related minerals for green house gas
removal. The reaction path involving carbonation of brucite (Mg(OH)2) is particularly
complex, as Mg has a strong tendency to form a series of metastable hydrous
carbonates. These metastable hydrous carbonates include hydromagnesite
(Mg5(CO3)4(OH)2.4H2O, or Mg4(CO3)3(OH)2.3H2O), artinite (Mg2CO3(OH)2.3H2O),
nesquehonite (MgCO3.3H2O), and lansfordite (MgCO3.5H2O). The free energy of
formation for these hydroxy and hydrous carbonates differ and their formation
depends on the partial pressure of CO2. In this work we report the synthesis of one of
these hydrous carbonate minerals namely hydromagnesite and the thermal stability
using dynamic and controlled rate thermal analysis (CRTA) of synthetic
hydromagnesite.

Experimental
Synthesis of hydromagnesite
The literature contains a number of methods for the synthesis of single phase
nesquehonite and hydromagnesite. Various authors [6, 56-59] have discussed the
effects of temperature and partial pressure of carbon dioxide pCO2 on the stability of
the synthetic products. A thermal stability study conducted by Lanas et al [14]
discussed the inherent difficulty associated with studying the MgO-CaO-H2O-CO2
system as there are multiple complex minerals which can form during the
dolomitization process. Synthetic hydromagnesite used in this study were synthesised
by the wet chemical method which involved selective precipitation of each mineral by
varying the carbonate buffering solution.
It was found that nesquehonite was preferentially precipitated from solution when
equimolar amounts of 0.5M Mg(NO3)2 and 0.5M 100% HCO3- solutions were mixed
drop wise over a period of 10 minutes at controlled reaction temperature of 45oC. The
precipitate was then transferred to a centrifuge to be spun down. At this point it is
interesting to note that the precipitate dissolved forming a clear solution. The liquor
was left in the centrifuge tube for a week and a new precipitate was found to have
formed producing large crystals. It is hypothesised that the initial precipitate was in
fact MgHCO3 although subsequent experiments failed to trap the initial precipitate for
analysis. Hydromagnesite was synthesised in a similar method to that of
nesquehonite. Only the carbonate solution was replaced with a 0.5M 100% CO32stock solution. Reaction parameters otherwise were identical to that of the
nesquehonite synthesis. The precipitate was centrifuged to separate from the mother
liquor and was then washed three times. The following reactions are envisaged to
occur:
Mg(NO3)2 + 2 NaHCO3 Mg(HCO3)2 + 2 NaNO3
Mg(HCO3)2 + 2H2O MgCO33H2O + CO2

The synthesised mineral was characterised for phase specificity using XRD,
and chemical composition by EDX methods.
Thermal Analysis
Dynamic experiment
Thermal decomposition of the hydromagnesite was carried out in a
Derivatograph PC type thermoanalytical equipment (Hungarian Optical Works,
Budapest, Hungary) capable of recording the thermogravimetric (TG), derivative
thermogravimetric (DTG) and differential thermal analysis (DTA) curves
simultaneously. The sample was heated in a ceramic crucible in static air atmosphere
at a rate of 5 C /min.
Controlled Rate Thermal analysis experiment
Thermal decomposition of the hydromagnesite was carried out in a
Derivatograph PC-type thermoanalytical instrument in an open ceramic crucible in
static air atmosphere at a pre-set, constant decomposition rate of 0.10 mg/min. (Below
this threshold value the samples were heated under dynamic conditions at a uniform
rate of 1C/min). With the quasi-isothermal, quasi-isobaric heating program of the
instrument the furnace temperature was regulated precisely to provide a uniform rate
of decomposition in the main decomposition stage.

Results and discussion

Dynamic thermal analysis of hydromagnesite
The dynamic thermal analysis of hydromagnesite is shown in Figure 1 where
the TG, DTG and DTA patterns are reported. Thermal decomposition in the TG
patterns occurs at four temperatures at 135, 184, 417 and 474C with mass losses of
6.7, 23.9, 15.6 and 17.6%. The results of the dynamic thermal analysis are reported in
Table 1. The total mass loss as determined by the TG analysis is 63.8%. The
theoretical mass loss based upon the formula above is 56.7%, made up of 37.8% for
decarbonation, 15.5% for water loss and 3.7% for dehydroxylation. Thus the
experimental mass loss is greater than the theoretical mass loss. The first two thermal
decomposition steps are attributed to dehydration and dehydroxylation. The last two
steps are assigned to the decarbonation.
The decomposition takes place as the follows:
Mg5[(CO3)4(OH)2].4H2O Mg5[(CO3)4(OH)2] + 4H2O
Mg5[(CO3)4(OH)2] 4 MgCO3 + MgO + H2O
4 MgCO3 4 MgO + 4CO2
In the DTA patterns endotherms are observed at 137, 187 417 and 474C, the
values of which correspond to the mass loss steps in the TG curves. These values
appear to differ from those reported by Beck [1]. Beck found the DTA patterns to start
slowly at 275C up to 325C with the loss of water of crystallisation. The loss of CO2
was reported to begin at 485 and reached a doublet at 565 and 600C [1]. The results
of Beck are so significantly different that the measurement is open to question. Beck
also claims that the product of the reaction is amorphous MgO which changes to a

cubic structure through an exothermic step at 510C. However no exothermic step

was observed in our DTA pattern. The difference may be due to the way in which the
experiments were conducted.
It is very interesting to compare the dynamic thermal analysis of nesquehonite
with hydromagnesite (Figure 2). In the DTA patterns for nesquehonite endotherms are
observed at 165, 195, 425 and 487C. The endotherms occur at very similar
temperatures. This observation leads to the conclusion that the mechanism for the
decomposition of nesquehonite is very similar to that of hydromagnesite. Davies and
Bubelba reported that a synthetic nesquehonite decomposed to hydromagnesite
through an intermediate phase which has an XRD pattern of dypingite [60].

Controlled rate thermal analysis of hydromagnesite

The CRTA pattern of hydromagnesite is shown in Figure 3. Five thermal
decomposition steps are observed in the CRTA pattern. The result summary is
reported in Table 2. There is a quasi-isothermal step at 100C followed by a second
decomposition step at 145C. As for the dynamic experiment these two steps are
attributed to dehydration as is confirmed by ion current curves for gas evolution. A
third decomposition step is observed at 203C as the only difference between the
decomposition patterns of hydromagnesite and nesquehonite. Due to the difference in
stochiometric composition between the two minerals, this additional peak can only
belong to the dehydroxylation of hydromagnesite.
There is an isothermal decomposition step at 370C which is ascribed to CO2
evolution. A second, sharp isothermal step at 409C is also observed in the DTG
curve. One possible assignment of this peak is to the decomposition of MgCO3
recrystallized from an amorphous to a cubic structure as was suggested by Beck in the
dynamic DTA experiment. The recrystallized carbonate structure decomposes at a
higher temperature. It is noted that the CRTA of nesquehonite (Figure 4) is very
similar to that of hydromagnesite as is the results of the dynamic TG experiment of
hydromagnesite and nesquehonite. If a comparison of the data is made, nesquehonite
CRTA pattern shows a quasi-isothermal dehydration steps at 108 followed by a nonisothermal dehydration step at 145C and a long time isothermal step at 376C.
Differences may be observed in the CRTA patterns of hydromagnesite and
nesquehonite at 203C attributed to the dehydroxylation of the hydromagnesite and
around 409C.

Conclusions
CRTA technology offers better resolution and a more detailed interpretation of
the decomposition processes of magnesium carbonate minerals such as
hydromagnesite via approaching equilibrium conditions of decomposition through the
elimination of the slow transfer of heat to the sample as a controlling parameter on the
process of decomposition. The CRTA experiment proves the thermal decomposition
of hydrated magnesium carbonates from different sources are almost identical. The
CRTA technology offers a mechanism for the study of the thermal decomposition of
minerals such as hydromagnesite and nesquehonite.

Acknowledgements
This research was supported by the Hungarian Scientific Research Fund (OTKA)
under grant No. K62175. The financial and infra-structure support of the Queensland
University of Technology Inorganic Materials Research Program is gratefully
acknowledged.

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List of Tables
Table 1

Mass loss and temperature data of hydromagnesite decomposition

under dynamic conditions

Table 2

Mass loss and temperature data of hydromagnesite decomposition

under CRTA conditions

List of Figures

Figure 1 Dynamic thermal analysis curves of hydromagnesite

Figure 2 Controlled rate thermal analysis curves of hydromagnesite
Figure 3 Dynamic thermal analysis curves of nesquehonite
Figure 4 Controlled rate thermal analysis curves of nesquehonite

Decomposition process
Dehydration and
dehydroxylation
Decarbonation and mineral
destruction

Hydromagnesite
Temp.
Mass loss
range (C) mg
%
24-140
3.4
6.7
140-294
12.2 23.9
294-436
8.0
15.6
436-498
9.0
17.6
498-855
0.7
1.4

Table 1. Mass loss and temperature data of hydromagnesite decomposition

under dynamic conditions

Decomposition process
Dehydration
Dehydroxylation
Decarbonation

Hydromagnesite
Sample mass: 99.62 mg
Temp.
Mass loss
range (C) mg
%
25-121
10.0 10.0
121-181
15.1 15.1
181-274
6.8
6.8
274-394
30.0 30.1
394-508
4.8
4.8

Table 2. Mass loss and temperature data of hydromagnesite decomposition

under CRTA conditions

10

Figure 1. Dynamic thermal analysis curves of hydromagnesite

Figure 2. Controlled rate thermal analysis curves of hydromagnesite

11

Figure 3. Dynamic thermal analysis curves of nesquehonite

Figure 4. Controlled rate thermal analysis curves of nesquehonite

12